Oil repellent compositions, methods for making same and textiles treated therewith



United States Patent 011.. REPELLENT COMPOSITIONS, METHODS FOR MAKHJGSAME AND TEXTILES TREATED TI-IEREWITH Domenick Donald Gagliardi, EastGreenwich, R.I., as-

signor to Colgate-Palmolive Company, New York, N.Y., a corporation ofDelaware No Drawing. Filed Sept. 30, 1963, Ser. No. 312,296

20 Claims. (Cl. 117-121) The present invention relates to thepreparation of water-, oil-, and soil-repellent hydrophilic oxides andto textiles, including fibers, yarns, woven materials, felted materials,and leather treated therewith. More particularly, the present inventionrelates to the treatment of cationic oxides, water-insoluble inorganicoxides such as alumina, titania, zirconia, silica, Zinc oxide and thelike to provide treated oxide which is resistant to wetting by water,waterborne stains, oil, oil-borne stains, and to soiling by oily treatedwith the aforesaid cationic oxides to impart to said particulate soiland to fibrous materials, e.g., textiles treated with the aforesaidcationic oxides to impart to said fibrous materials the capability ofresisting wetting by water and/ or oil.

It has been known to coat regenerated cellulose products and moreparticularly filaments and staple fibers of viscose rayon to depositthereon finely divided silica to improve the resistance of the fiber tosoiling. However, the deposited silica, particularly that deposited onthe outer surface of the fiber and not in the fiber crevices, has atendency to become disassociated from the fiber during opening, carding,drawing and other such mechanical operations in which the coated fibersrub one against the other. In U.S. Patent No. 2,983,625 an improvementis disclosed wherein the fiber containing the silica deposited thereonis treated with alkylene oxide products of polyhydroxy alcohol esters ofhigher fatty acids whereby the fiber is substantially improved withrespect to carding, drafting, softness, and hand or feel and the amountof silica retention without dusting for any particular method ofdepositing the silica on the fiber is substantially increased.

In U.S. Patent No. 3,031,335 there is disclosed a method of producingoiland water-resistant fabrics in a twostep process involving immersionof the fabric in a solution of a salt such as aluminum acetate,zirconium nitrate, zirconium butoxide, drying the fabric, and immersingthe dried fabric in a solution of perfiuoromonocarboxylic acid, such asperfluorooctanoic acid, perfluorodecanoic acid, or one of the saltsthereof. As illustrated the finished fiber consists of the fiber core, alayer of the aluminum or zirconium salt, and superposed thereon a secondlayer of the perfluoromonocarboxylic acid or salt.

In distinct contrast to the aforedescribed product, the product of thepresent invention is a waterand oil-repellent as well as soil-repellentfiber or textile which in its simplest form consists of a core offibrous material and a single layer of the treated cationic inorganicoxide.

In general, a water-soluble cationic oxide such as alumina, titania,zirconia, silica, zinc oxide, or mixtures of such water-insolublecationic oxides, for example, bentonites, clays and the like in finelydivided state is reacted with at least one fluorinated aliphaticmonocarboxyl- "ice ic acid having four to twenty-two carbon atoms inwhich at least percent to 100 percent of the non-carbon-to carbonvalences of the non-carboxylic carbon atoms is attached to fluorineatoms and has at least two and preferably three fluorine atoms attachedto the terminal or omega carbon atom. In general, theperfluoroalkylmonocarboxylic acids have a composition corresponding tothe formula:

X(CF COOH where X is CHF or CF n is 3 to 20 and percent F=at least 70%[X|(CH Thus, for example fifty parts by weight of finely dividedaluminum oxide were mixed with five hundred parts by weight ofisopropanol (a solvent for the perfluoro aliphatic monocarboxylic acid)and four parts by weight of pentadecafluorooctanoic acid(perfiuorooctanoic acid). The reaction mixture was refluxed at 82.5 C.for one hour and cooled to room temperature. The cooled reaction mixturewas filtered, the white filter cake was washed with alcohol and dried.Gravimetric analysis established that the aluminum oxide had combinedwith about 5.6 percent of the perfluorooctanoic acid based upon theweight of aluminum oxide used.

Illustrative of the preparation of the treated cationic inorganic oxideand a method of applying the reaction product to textile material is thetreatment of alumina with pentadecafluorooctanoic acid and the paddingof cotton with the reaction dispersion. Alumina was reacted withpentadecafluorooctanoic acid in isopropanol in the ratios of 1:1, 10:1,100:1, and 1,000z1 by weight at reflux temperature (about 82 C.) forabout one hour. The reaction mixtures were cooled and x 80 cotton paddedwith the cooled dispersions to 80 percent wet pick-up. The treatedcotton was dried 24 hours at room temperature. The so-treated cotton anduntreated cotton were subjected to the Oily Particulate Soil Repellencytest described hereinafter with the results set forth in Table I.

The data presented in Table I makeit manifest that the treated cottonsheds oily particulate soil.

Alternatively, the reaction product, i.e., the per-fluoroacid treatedcationic oxide is separated from the reaction mixture, washed with asolvent for the perfiuoroacid, suspended in water with or without asurfactant and the textile padded or otherwise treated with the aqueousdispersion.

The water and oil repellency properties of alumina particles treatedwith various perfluoromonocarboxylic acids are shown in Table I. Theoriginal alumina particles had a water and oil repellency rating ofzero.

Illustrative of the waterand oil-repellency properties conferred oncationic water-insoluble inorganic oxides per so by treatment withperfluoromonocarboxylic acids are the data presented in Table IIobtained from the treatment of alumina particles with variousperfluoromonocarboxylic acids. The untreated particles of aluminaRating: Characterized by 7 had Water and ml'repenency rating of Zero 80Wetting of the supper surface at spray points. 7

TABLE II ReactionMixture Filtered, Cake ReactionMixtui-e Fil- ReactionProduct Dried Down Reaction Mixture Filtered and Washed with IPA,Filtered and tered, Cake Washed with Cake Dried Dried Acetone, Filteredand Dried Weight Ratio of Alumina to Pertluoro acid Oil 1 Water 2 OilWater Oil Water Oil Water NG G NG G NG G NG G NG G NG G NG G NG G Samerating system as that of 3M oil-heptane test described hereinafter.

2 Rating applying water drop to treated cloth with medicine dropper.

100-dr0p rolled off. 90-drop did not penetrate in three minutes.

Alumina and pentadecafluorooctanoic acid were reacted for about one hourat reflux temperature (about 80 C.) in isopropanol. The reaction productwas padded on cotton (80 X 80) from isopropanol or water suspension'anddried. The oil repellency and resistance to soiling with oilyparticulate soil were determined. The results are presented in TableIII.

IPA-Isopropanol.

It will be observed that in every instance the treated .cloth'beforewashing had a higher reflectance than the untreated cloth. In otherwords, the treated cloth shed 'the oily particulate soil. Furthermore,it will be noted 'thattreated cloth when cured at room temperature hadexcellent oil repellency;

i It is manifest that controlled evaluating of fabric finishes in actualuse is not possible. Consequently, it has been. necessary to useevaluation methods subject to -laboratory control which will simulate asclosely as possible actual conditions under which water-repellency, oil

repellency, resistance to staining by Water-borne and oilborne stains;and resistance to staining by oilyparticulate soil of treated fabricsoccurs. Such methods of evaluation are the following:

Water Repellency.'-Resistance to wetting (spray test) AATCC StandardTest Method 221952 O-drop penetrated.

NGnot ground.

70 Partial wetting of the whole of the upper surface. 7

50 Complete wetting of the whole of the upper surface.

0 Complete wetting of the whole of the upp e and the lower surfaces.

The test specimens 'of minimum size of 7" x 7" (seven inches by seveninches) are conditioned at 70 F. and

65 percent relative humidity fora minimum of four hours 7 beforetesting.

The test specimen, fastened'securely and Wrinkle-free in a metal hoophaving a diameter of 6 inches, is placed and centered 6 inches under astandard spray nozzle at an angle of to the horizontal. Two hundred andfifty milliliters of water at 80:2 F. is poured intoa funnel attachedabove the spray nozzle. The spray lasts 25 to 30 seconds at the end ofwhich time the hoop is taken by one edge and the opposite edge tappedsmartly once against a solid object with the wet side facing the solid;this pro- 1 cedure is repeated with the hoop reversed 180.

Oil Repellency.-3M Textile Chemicals appendix A test methods, page 1 TheMinnesota Mining oil repellency test is based on the difierentpenetrating properties of the two hydro- This test is applicable to anytextilefabric. It measures' the resistance of fabrics to wetting by awater spray and the results depend primarily on the degree of hydro-.phobicity inherentin the fibers and yarns and subsequent @treatments towhich the fabric is subjected. Water is sprayed against the taut surfaceof a test specimen. Evalu ation of the wetted pattern is readily broughtabout by ,comparing the wetted pattern with standard wetting patternpictures:

Rating: I V Characterized by 100 No sticking or wetting of the uppersurface. 90 Slight random sticking or wetting of the upper surface.

carbon liquids, mineral oil (Nujol) and n-heptane. '(Nujol is the tradename for white mineral or paraflin oil being a mixture of hydrocarbonshavingra density for. light oil in the range of 0.83 to 0.860 and forheavy oil in the rangeof 0.875 to 0.905.) The Nujol-heptane proportionsfor each rating were selected by 3M to give borne stainresistancecorresponding to each of the spray ratings of the AATCCStandard Test Method 22-1952.

Oil Repel- Percent Hep- Percent lency tane (by Nujol (by Rating volume)volume) 1 No hold out to Nujol.

The standard oil-heptane mixtures are contained in small stopperedmedicine-dropper bottles. A d-rop of each'mixture of .Nujol and heptaneis placed 'on the fabric. The appearance'of the test oil is observedthrough the drop. 7 Note is made whether wetting or penetration. occurs.The number corresponding to that mixture containing the oily stainresistance somewhat comparable to the waterhighest percentage of heptanewhich does not penetrate or wet the fabric after three minutes isconsidered the oil repellency rating of the system.

The change in the optical refractivity of the drop is often anindication of wetting. In some cases wetting can be better determined byobserving the other side of the fabric. In some cases reportedhereinafter the term has been used to indicate a modicum of resistanceto wetting by oil.

Stain repellency The following procedures have been used to establishthe degree of resistance to staining by water-borne and oil-borne stainsof fabrics.

(a) The fabrics were stretched lightly on 12" x 31" frames. All or partof the fiame was used depending upon the amount of fabric available. Theframes were supported at both ends with the fabric about 8 inches abovea black surface. The fabric touched nothing.

(b) Three inch medicine droppers were used to draw the stains from thecontainers. A 1 cubic centimeter calibration was established and markedon the exterior of each dropper. The stains were squeezed verticallydownward from a height 2 inches above the cloth.

(c) After five minutes the unabsorbed stain was wiped off the fabricwith two sweeps of Kleenex and the stains rated as follows:

Appearance: Rating No stain visible Slight stain 4 Easily noticeablestain 3 Considerable stain 2 Very heavily stained 1 (The spread or lackof spread is not necessarily reflected in the ratings.)

(d) Duplicate sets of stains were applied in separate areas so thatone-half of the fabric could be washed. In most instances, the wash wascarried out with 50 grams of FAB, a cotton cycle, and a dummy load tototal 5 pounds in a Norge home automatic washer.

(e) The following two lists describe the numbering and the grosscharacterizations of the stains employed.

Water stains Instant Tea Sheaifers 232 Blue-black skrip A&P ConcordGrape Juice Ann Page Salad Mustard Bosco chocolate syrup Oilyparticulate soil repellency.-(GRC dry soil test) Fifteen to twenty 6" x8" numbered specimens (normally 80 x 80 cotton), including at least oneuntreated control, are tumbled for thirty minutes with 10 percent ofCyanamid Soil based on the weight of the fabric. The tumbling is carriedout in a 5 liter capacity Five Minute Home Cleaner at 44 r.p.m.; six No.8 neoprene rubber stoppers are distributed among the specimens toincrease the mechanical action. At the end of tumbling, the specimensare removed and each shaken separately up and down fifteen times by handto remove surface dirt.

The specimens are then cut in two (to produce two 4 x 6" pieces).One-half is washed with 50 grams of FAB in a cotton cycle with a S-pounddummy load, then hung to dry and lightly ironed under a clean cottoncloth.

The degree of soiling is determined with a Photovolt Reflectance Meter(Tri Blue Filter). Six readings per specimen are made and the arithmeticaverage reported.

The Cyanamid Soil described below is the same as that recommended byMinnesota Mining and Manufacturing Co. The following dry ingredients areblended throughly, dried in a forced draft convection oven for eighthours at 50 C., then milled for twenty-five hours with ceramic balls andstored in a polyethylene bag.

Material Percent by weight Peat moss 38 Cement 17 Kaolin clay 1 17Silica, 200 mesh 17 Furnace blaclt 1.75 Red iron oxide 4 0.50 Mineraloil 8.75

1 Peerless R. T. Vanderbilt.

2 Davidson Chemical Co.

3 Molacco Benny and Smith C0.

4 C. K. Williams Co.

The aforedescribed water-insoluble cationic inorganic oxides aftertreatment with perfluoromonocarboxylic acids are also useful fortreating other substrates, e.g., ceramics, leather, paper, elastomer,e.g., natural rubber, synthetic elastomers and plastics to confer uponor impart thereto the capability of resisting soiling by oilyparticulate-soil. These treated water-insoluble cationic inorganicoxides can also be used as fillers for resins and elastomers includingnatural rubber.

What is claimed is:

1. A method of producing oil-repellent finishing agent for textileswhich comprises heating a reaction mixture consisting essentially offrom 1 to 1000 parts by weight of a finely divided water-insoluble,hydrophilic cationic inorganic oxide, per one part of perfiuoroaliphaticmonocarboxylic acid and solvent for said perfluoroaliphaticmonocarboxylic acid at about the reflux temperature of said solvent,said perfluor-oaliphatic monocarboxylic acid being an aliphaticmonocarboxylic acid having four to twenty-two (inclusive) carbon atomsin the molecule of which at least seventy percent to one hundred percentof the non-carbon-to-carbon valences of the non-carboxylic carbon atomsis satisfied by fluorine atoms and at least two to three fluorine atomsare attached to the terminal carbon atom of the aliphatic chain of saidmonocarboxylic acid.

2. The method of producing oil-repellent finishing agent for textiles asset forth in claim 1 wherein the water-insoluble, hydrophilic, cationicinorganic oxide is alumina.

3. The method of producing oil-repellent finishing agent for textiles asset forth in claim 2 wherein the perfluoroaliphatic monocarboxylic acidis pentadecafluorooctanoic acid.

4. The method of producing oil-repellent finishing agent for textiles asset forth in claim 2 wherein the perfiuoroaliphatic monocarboxylic acidis CF (CF COOH.

5. The method set forth in claim 1 wherein the solvent is isopropanol.

6. A method of conferring oil-repellency as well as resistance tosoiling with oily, particulate soil on textile material which comprisespadding textile material to at least percent wet pick-up in a suspensionof water-insoluble, hydrophilic, cationic inorganic oxide treated withperfiuoroaliphatic monocarboxylic acid, and curing said treated textilematerial at a temperature in the range of room temperature to 350 F. fora time inversely proportioned to the temperature and about five minutesat 300 F., said perfluoroaliphatic monocarboxylic acid having four totwenty-two carbon atoms in the molecule in 8. The method of conferringoil-repellency as well as:

resistance to soiling with oily, particulate soil on textile material asset forth in claim 6 wherein the suspension of water-insoluble,hydrophilic, cationic inorganic oxide treated with perfluoroaliphaticmonocarboxylic acid con-,

tain's non-rewetting surfactant.

9. The method of conferring oil-repellency as well as resistance tosoiling with oily, particulate soil on textile material as set forth inclaim 6 wherein the suspension of water-insoluble, hydrophilic, cationicinorganic oxide treated with perfluoroaliphatic monocarboxylic acidcontains at least one percent of said treated inorganic oxide.

10. The method set forth in claim 6 wherein the treated cationicinorganic oxide is suspended in isopropanol.

11. The method set forth in 'claim 6 wherein the treated cationicinorganic oxide is suspended in water.

12. A method of conferring oil-repellency as well as resistance tosoiling with oily, particulate soil on textile material which comprisesheating a reaction mixture comprising water-insoluble, hydrophilic,cationic inorganic oxide, perfluoroaliphatic monocarboxylic acid andsolvent for said perfluoroaliphatic monocarboxylic acid at about thereflux temperature of said solvent, padding textile material to at least70 percent wet pick-up in said reaction mixture, and curing the treatedtextile at a temperature in the range of room temperature to 350 F. fora time inversely proportioned to the temperature and about five minutesat 300 F., said perfluoroaliphatic monocarboxylic acid having four totwenty-two carbon atoms in the molecule of which at least seventy to onehundred percent of the non-carbon-to-carbon valences of thenon-carboxylic carbon atoms is satisfied by florine atoms.

8 13. The method set forth in claim 12 wherein the solvent isisopropanol.

i 14. An oil repellent composition consisting essentially of thereaction product of 1 to 1000 parts by weight of .a finely dividedwater-insoluble inorganic oxide with at least one part ofperfluoroaliphatic monocarboxylic acid containing from 4 to-22 carbonatoms of which at least percent to percent of the non-carbon-to-carbonvalences of the non-carboxylic carbon atoms is saitsfied by fluorineatoms and at least 2 to 3 fluorine atoms'are attached to the terminalcarbon atom of the aliphatic chain of said non-carboxylic acid.

' 15. An oil repellent composition as defined in claim 14 wherein saidinorganic oxide is alumina.

16. An oil repellent article comprising a fibrous material havingaflixed thereto as an oil repellent surface a composition as defined inclaim 14.

17. An oil repellent composition as defined in claim 15 wherein theperfluoroaliphatic monocarboxylic' acid is pentadecafluo'rooctanoicacid. 1

18. -An oil repellent article as defined in claim 16 wherein the fibrousmaterial is a textile material.

19. An oil repellent article as defined in claim 16 wherein the fibrousmaterial is leather. 7 a 20. An oil repellent article as defined inclaim 16 wherein the fibrous material is paper.

7 References Cited UNITED STATES PATENTS WILLIAM D. MARTIN, PrimaryExaminer. MURRAY KATZ, Examiner- T. G. DAVIS, Assistant Examiner.

1. A METHOD OF PRODUCING OIL-REPELLENT FINISHING AGENT FOR TEXTILES WHICH COMPRISES HEATING A REACTION MIXTURE CONSISTING ESSENTIALLY OF FROM 1 TO 1000 PARTS BY WEIGHT OF A FINELY DIVIDED WATER-INSOLUBLE, HYDROPHILIC CATIONIC INORGANIC OXIDE, PER ONE PART OF PERFLUOROALIPHATIC MONOCARBOXYLIC ACID AND SOLVENT FOR SAID PERFLUOROALIPHATIC MONOCARBOXYLIC ACID AT ABOUT THE REFLUX TEMPERATURE OF SAID SOLVENT, SAID PERFLUOROALIPHATIC MONOCARBOXYLIC ACID BEING AN ALIPHATIC MONOCARBOXYLIC ACID HAVING FOUR TO TWENTY-TWO (INCLUSIVE) CARBON ATOMS IN THE MOLECULE OF WHICH AT LEAST SEVENTY PERCENT TO ONE HUNDRED PERCENT OF THE NON-CARBON-TO-CARBON VALENCES OF THE NON-CARBOXYLIC CARBON ATOMS IS SATISFIED BY FLUORINE ATOMS AND AT LEAST TWO TO THREE FLUORINE ATOMS ARE ATTACHED TO THE TERMINAL CARBON ATOM OF THE ALIPHATIC CHAIN OF SAID MONOCARBOXYLIC ACID. 